CN109021614A - Double chromogen reactive dye of a kind of high colour-fast rate phthalocyanine azo group and its preparation method and application - Google Patents

Double chromogen reactive dye of a kind of high colour-fast rate phthalocyanine azo group and its preparation method and application Download PDF

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CN109021614A
CN109021614A CN201811004414.6A CN201811004414A CN109021614A CN 109021614 A CN109021614 A CN 109021614A CN 201811004414 A CN201811004414 A CN 201811004414A CN 109021614 A CN109021614 A CN 109021614A
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reaction
reactive dye
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CN109021614B (en
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侯爱芹
谢孔良
胡柳
高爱芹
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Donghua University
National Dong Hwa University
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Donghua University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
    • C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
    • C09B62/10—Porphines; Azaporphines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0003—Drying, e.g. sprax drying; Sublimation of the solvent
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
    • D06P1/382—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group directly attached to heterocyclic group
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • D06P3/663—Natural or regenerated cellulose using reactive dyes reactive group directly attached to heterocyclic group

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coloring (AREA)

Abstract

The present invention relates to double chromogen reactive dye of a kind of high colour-fast rate phthalocyanine azo group and its preparation method and application, are to prepare the bright blue color base of phthalocyanine by copper phthalocyanine chlorosulfonation, primary condensation, secondary condensation, diazo-reaction, coupling reaction obtain the high colour-fast rate reactive dye of a class formation.The present invention is suitable for cotton, synthetic cotton, fiber crops, regenerated fiber and their printing in textiles, which has high colour-fast rate, bright in color light, excellent enhancing and good washable, colour fastness to rubbing, have a good application prospect.

Description

Double chromogen reactive dye of a kind of high colour-fast rate phthalocyanine azo group and preparation method thereof and Using
Technical field
The invention belongs to reactive dyestuff field, in particular to a kind of double chromogen reactive dye of high colour-fast rate phthalocyanine azo group And its preparation method and application.
Background technique
Since reactive dye come out, it has also become most important dye class in cotton reactive dye, bright in colour, chromatography Complete, low in cost, development is constantly in critical role.Reactive dyestuff molecule is by water soluble group, dye matrix, linker, Active group is constituted, and hydrolysis can occur for dye molecule to lose the ability with fiber-reactive in application process, reduces dyestuff Utilization rate, while the waste water from dyestuff discharged can cause ecological, environmental protective problem, also there is certain harm to human body.Therefore exploitation Gao Gu The new reactive dyes of color rate have great importance.Copper phthalocyanine reactive dye occupy critically important position in reactive dye, Copper phthalocyaine dye bright in color light, molar extinction coefficient is high, has excellent color fastness to light, but copper phthalocyaine dye is to fiber parent Low with power, degree of fixation is low, and traditional emerald green blue degree of fixation of No. 21 activity of copper phthalocyanine only has 40-50%, and dye utilization rate is low, and dyeing is dirty Water discharge amount is big, and waste water advanced depth, dyestuff level-dyeing property is poor, is unfavorable for the clean manufacturing of printing and dyeing.It is badly in need of invention high colour-fast rate, usury With the copper phthalocyanine reactive dye of rate.Develop a kind of high colour-fast rate phthalocyanine azo mixing chromogen reactive dye and be one and important grinds Study carefully direction, is of great significance to printing and dyeing clean manufacturing.
Summary of the invention
The present invention provides double chromogen reactive dye of a kind of high colour-fast rate phthalocyanine azo group and its preparation method and application, The reactive dye solve the not high technical problem of current copper phthalocyanine reactive dye color fixing rate.
The present invention provides the double chromogen reactive dye of a kind of high colour-fast rate phthalocyanine azo group, it is characterised in that: structure is logical Formula is as follows:
In formula, 0 < x≤2,0 < y≤2,0 z≤2 <, and x+y+z=3.5~4.
The present invention also provides the preparation methods of the double chromogen reactive dye of a kind of high colour-fast rate phthalocyanine azo group, comprising:
(1) under room temperature, chlorosulfonic acid is added into reaction vessel, copper phthalocyanine is added under stirring at room temperature, carries out sulfonation And chlorination reaction is added thionyl chloride reaction, reaction system is added in ice water, suction filtration obtains copper phthalocyanine sulphur after reaction Acyl；Wherein, the molar ratio of copper phthalocyanine, chlorosulfonic acid and thionyl chloride is 1~2:40~50:20~25；
(2) it by the copper phthalocyanine sulfonic acid chloride wiring solution-forming in step (1) and is beaten, 2,4- diamino benzene sulfonic acid sodium solution is added It is reacted with pyridine, adding ammonium hydroxide, the reaction was continued, obtains turquoise blue based sols；Wherein, copper phthalocyanine sulfonic acid chloride, 2,4- diaminobenzene The molar ratio of sodium sulfonate and ammonium hydroxide is 1:1~2:1~3；
(3) it by Cyanuric Chloride wiring solution-forming and is beaten, the turquoise blue based sols being added in step (2) are stirred to react, and are obtained One contracting object；Wherein, the molar ratio of bright blue color base and Cyanuric Chloride is 1:1.02~2.04；
(4) 2,4- diamino benzene sulfonic acid sodium is added in step (3) described contracting object solution and is stirred to react, obtain two contractings Object；Wherein, a contracting object and 2, the molar ratio of 4- diamino benzene sulfonic acid sodium are 1:1~2；
(5) two contracting things solution described in step (4) is cooled down under ice-water bath, concentrated hydrochloric acid is added, and instill sodium nitrite Solution, being kept for -5~0 DEG C after dripping off, the reaction was continued 1.5~2 hours, obtains diazonium salt；Wherein, two contracting things, concentrated hydrochloric acid and nitrous The molar ratio of sour sodium is 1:2~3:1~2；
(6) it by Cyanuric Chloride wiring solution-forming and is beaten, Rn is added1Solution reaction obtains Rn1One contracting object, after the reaction was completed plus Enter Rn2Dry powder obtains Rn1Two contracting things；Wherein, Rn1, Cyanuric Chloride and Rn2Molar ratio be 1:1.02:1；
(7) it will be added in diazonium salt described in step (5) after the cooling of two contracting things described in step (6), carry out coupling reaction, ?；Wherein, the molar ratio of diazonium salt and two contracting things described in step (6) is 1:1~2.
Sulfonation temperature in the step (1) is 130~140 DEG C, and sulfonation time is 3~6h；Chlorination temperature is 90~105 DEG C, time of chlorinating is 1~3h.
The mass fraction of copper phthalocyanine chloride solution in the step (2) is 10~20%, and mashing temperature is 0~5 DEG C, Time is 50~70min；The mass fraction of 2,4- diamino benzene sulfonic acid sodium solution is 10%~20%.
Reaction condition after addition 2,4- diamino benzene sulfonic acid sodium in the step (2) are as follows: pH value is 6.5~7,10~20 DEG C Under conditions of react 5~7h；Reaction condition after addition ammonium hydroxide are as follows: pH value is 9~10,30-35 DEG C, reacts 4~5h, exists again later PH value is 9~10,40~50 DEG C of 2~3h of reaction.
The mass fraction of Cyanuric Chloride solution in the step (3) is 10~20%, and mashing temperature is 0~2 DEG C, mashing Time is 20~40min；Turquoise blue based sols are cooled to 5 DEG C hereinafter, pH value is down to 6 in advance；Reaction temperature is 0~10 DEG C, is adjusted Section pH value is 3-5, and the reaction time is 7~12h.
Reaction temperature in the step (4) is 35~40 DEG C, and adjusting pH value is 7~9, and the reaction time is 10~12h.
The mass fraction of Cyanuric Chloride solution in the step (6) is 10~20%, and mashing temperature is 0~2 DEG C, mashing Time is 20~40min；One contracting reaction temperature is 0~5 DEG C, and pH value in reaction is 3~3.5, and the reaction time is 1~2h；Two contractings are anti- Answering temperature is 30~35 DEG C, and pH value in reaction is 4~4.5, and the reaction time is 5~6h.
Rn in the step (6)1For 1- amino-8-naphthol -3,6- disulfonic acid sodium salt, 2- amino -5- hydroxyl -7- naphthalene sulphur Acid or 1- hydroxyl -7- amino -3- naphthalene sulfonic acids；Rn2For 4- β-ethyl sulfuryl sulfate ester aniline or 3- β-ethyl sulfuryl sulfuric ester benzene Amine.
Coupling reaction temperature in the step (7) is 10~15 DEG C, and pH value is 5.5~6.5, and the reaction time is 6~7h.
The present invention also provides the applications of the double chromogen reactive dye of a kind of high colour-fast rate phthalocyanine azo group, by doing by spraying Power-product is made after dry processing.
The double chromogen reactive dye of high colour-fast rate phthalocyanine azo group of the present invention can also contain some other dye Expect component and partial impurities because dyestuff be conventionally synthesized or salting-out process in inevitably with fraction impurity dyestuff and Electrolytic powder (sodium chloride etc.), the presence of these substances has no effect on technical effect of the invention.
The present invention also provides a kind of high colour-fast rate reactive dye compound stamps of the textile fabrics such as cotton, fiber crops, regenerated fiber Dyestuff.
Beneficial effect
(1) present invention greatly improves copper phthalocyaine dye to fiber by introducing conjugation azo group in copper phthalocyanine intramolecular The affinity of cellulose fiber has obtained a kind of degree of fixation close to 100% reactive dye；
(2) present invention by introducing phthalocyanine and azo mixing color development system, structure novel, Molar Extinction simultaneously in the molecule The problems such as coefficient is high, overcomes the compatibility and poor color fastness of dyestuff colorant match；
(3) the high colour-fast rate reactive dye that are prepared of the present invention for cotton, fiber crops, regenerated fiber fabric stamp, have High dye utilization rate, good lifting force and excellent every color fastness, has a good application prospect.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of high colour-fast rate reactive dye in embodiment 1；
Fig. 2 is the infrared spectrogram of high colour-fast rate reactive dye in embodiment 2；
Fig. 3 is the infrared spectrogram of high colour-fast rate reactive dye in embodiment 3；
Fig. 4 is the ultraviolet-visible absorption spectroscopy figure of high colour-fast rate reactive dye in embodiment 4；
Fig. 5 is printing fixation curve of the high colour-fast rate reactive dye on cotton fabric in embodiment 5；
Fig. 6 is that stamp of the high colour-fast rate reactive dye on cotton fabric promotes force curve in embodiment 5.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Range.
Embodiment 1
The synthesis of the following high colour-fast rate mixing chromogen reactive dye of structure:
(1) preparation of copper phthalocyanine sulfonic acid chloride: under room temperature, to three mouthfuls equipped with reflux condensing tube and device for absorbing tail gas 80mL chlorosulfonic acid is added in flask, 15g copper phthalocyanine is added under stiring, then raises temperature to 135 DEG C of reaction 5h, then be cooled to 60 DEG C 22mL thionyl chloride is added thereto, then heats to 100 DEG C of reaction 2h, is cooled to 30 DEG C later hereinafter, system is being stirred In the case where be slowly added in ice water, filter, filter cake washs with appropriate ice water, obtains copper phthalocyanine sulfonic acid chloride filter cake 58g.
(2) preparation of the bright blue color base of copper phthalocyanine: the copper phthalocyanine sulfonic acid chloride in step (1) is beaten under the conditions of ice-water bath 1h.Accurately weigh 5.04g 2,4- diamino benzene sulfonic acid sodium (double) is made into 15% solution, with sodium carbonate adjust pH value be 6~ 6.5, it is added drop-wise in the uniform copper phthalocyanine sulfonic acid chloride of mashing dropwise, appropriate pyridine is added and makees catalyst.It is 6.5~7,15 in pH value 7h is reacted under conditions of~20 DEG C, the ammonium hydroxide of 30-35 DEG C of addition 1.03mL 20% is warming up to, then reacts 5h, pH value is risen to 9~10, temperature rises to 40~45 DEG C of reaction 3h, detects reaction end using thin-layered chromatography.
(3) preparation of bright blue one contracting object of color base: the solution that 5.11g Cyanuric Chloride is made into 20% is weighed, in 0~2 DEG C of condition Under 30min is beaten in ice water.Turquoise blue based sols in step (2) are cooled to 5 DEG C hereinafter, pH value is down to 6, are instilled dropwise In Cyanuric Chloride, reaction temperature is 0~10 DEG C, and pH value in reaction is 4~5, and reaction time 12h is detected using thin-layered chromatography Reaction end.
(4) preparation of two contracting things: by 5.04g 2,4- diamino benzene sulfonic acid dry powder is added in step (3) described contracting liquid, 35~40 DEG C are warming up to, pH rises to 7~8, reacts 7h, detects reaction end using thin-layered chromatography.
(5) step (4) the two contracting liquid of copper phthalocyanine the preparation of diazonium salt: is cooled to 5 DEG C hereinafter, being added under ice-water bath The concentrated hydrochloric acid solution that 5.20g mass fraction is 36.5%, it is water-soluble to be slowly dropped into 1.82g sodium nitrite is made into 30% in 1h Liquid reacts 1.5h under the conditions of -5~0 DEG C after dripping off.
(6) it the preparation of a contracting object and two contracting things of 1- amino-8-naphthol -3,6- sodium disulfonate: is carried out in above-mentioned reaction Meanwhile the solution that 5.11g Cyanuric Chloride is made into 20% is weighed, 30min is beaten in ice water under the conditions of 0~2 DEG C.It will 10.26g1- amino-8-naphthol -3,6- disulfonic acid is made into 15% solution, adjusts pH 5.8~6.0, instills three polychlorostyrene dropwise In cyanogen, 1h is reacted under the conditions of 0~5 DEG C and pH value are 3~3.5, detects reaction end using thin-layer chromatography.One contracting reaches reaction After terminal, 7.62g 4- β-ethyl sulfuryl sulfate ester aniline (para-ester) dry powder is added into a contracting object, is warming up to 30~35 DEG C, PH value is adjusted to 4~4.5, reacts 5h, detects reaction end using thin-layer chromatography.
(7) coupling reaction: the two contracting things in above-mentioned (6) are cooled at 5 DEG C, and the copper phthalocyanine prepared in (5) is added later In diazonium salt, at 10~15 DEG C, under conditions of pH value is 5.5~6.5, reaction time 7h detects reaction eventually using thin-layer chromatography Point.Obtained product is dried at a temperature of 65 DEG C, obtains high colour-fast rate reactive dye.Yield 63%, dyestuff is through saltouing, DMF- CH2Cl2Recrystallization purification, infrared spectroscopy are shown in Fig. 1.
Dyestuff is in 3334.35cm-1Strong broad peak be N-H and OH stretching vibration formed broad peak；In 2989.34 weak absorptions Peak is CH2Stretching vibration absworption peak；1544.61cm-1Be absorbed as C=N stretching vibration absworption peak；1483.73cm-1Absorption For phenyl ring characteristic absorption peak；1391.10cm-1Be absorbed as C-N stretching vibration absworption peak on iso-indoles ring；1323.02cm-1's Absorption peak is S=O stretching vibration and the broad peak that phthalocyanine ring characteristic absorption is formed；1138.15 1088.35cm-1With 1037.35cm-1For the characteristic absorption peak of phthalocyanine ring；741.27cm-1For the stretching vibration peak of C-S and C-Cl；907.86cm-1For Cu-N vibration absorption peak.
Embodiment 2
The synthesis technology of the following high colour-fast rate mixing chromogen reactive dye of structure:
(1) preparation of copper phthalocyanine sulfonic acid chloride: under room temperature, to three mouthfuls equipped with reflux condensing tube and device for absorbing tail gas 80mL chlorosulfonic acid is added in flask, 15g copper phthalocyanine is added under stiring, then raises temperature to 135 DEG C of reaction 5h, then be cooled to 60 DEG C Thereto be added 22mL thionyl chloride, be warming up to 100 DEG C of reaction 2h, be cooled to later 30 DEG C hereinafter, by system stirring feelings It is slowly added in ice water, filters under condition, filter cake is washed with appropriate ice water, obtains copper phthalocyanine sulfonic acid chloride filter cake 58g.
(2) preparation of the bright blue color base of copper phthalocyanine: the copper phthalocyanine sulfonic acid chloride in step (1) is beaten under the conditions of ice-water bath 1h.Accurately weighing 5.04g 2,4- diamino benzene sulfonic acid sodium salt (double) is made into 15% solution, and adjusting pH value is 6~6.5, by It is added drop-wise in the uniform copper phthalocyanine sulfonic acid chloride of mashing, appropriate pyridine is added and makees catalyst.It is 6.5~7,15~20 DEG C in pH value Under conditions of react 7h, be warming up to 30-35 DEG C of addition 1.03mL ammonium hydroxide reaction 5h, pH value risen into 9~10 temperature later and is risen to 40~45 DEG C of reaction 3h detect reaction end using thin-layered chromatography.
(3) preparation of bright blue one contracting object of color base: the solution that 5.11g Cyanuric Chloride is made into 20% is weighed, in 0~2 DEG C of condition Under 1h is beaten in ice water.Turquoise blue based sols in step (2) are cooled to 5 DEG C hereinafter, pH value is down to 6, instill three dropwise In polychlorostyrene cyanogen, reaction temperature is 0~10 DEG C, and pH value in reaction is 4~5, reaction time 12h, is detected using thin-layered chromatography anti- Answer terminal.
(4) step (3) described contracting liquid preparation of two contracting things: is added in 5.04g 2,4- diamino benzene sulfonic acid sodium salt dry powder In, 35~40 DEG C are warming up to, pH rises to 7~8, reacts 7h, detects reaction end using thin-layered chromatography.
(5) step (4) the two contractings liquid preparation of diazonium salt: is cooled to 5 DEG C hereinafter, 5.20g is added under ice-water bath The concentrated hydrochloric acid solution that mass fraction is 36.5%, 30% aqueous solution that 1.82g sodium nitrite is made into is slowly dropped into 1h, is dripped off 1.5h is reacted under the conditions of -5~0 DEG C afterwards.
(6) preparation of one contracting object and two contracting things of 2- amino -5- hydroxyl -7- naphthalene sulfonic acids: while above-mentioned reaction carries out, claim It takes 5.11g Cyanuric Chloride to be made into 20% solution, is beaten 30min in ice water under the conditions of 0~2 DEG C.By 10.26g1- amino- 8- naphthols -3,6- disulfonic acid is made into 15% solution, adjusts pH 5.8~6.0, instills in Cyanuric Chloride dropwise, at 0~5 DEG C 1h is reacted under the conditions of being 3~3.5 with pH value, detects reaction end using thin-layer chromatography.Reaction end is detected using thin-layer chromatography. After one contracting reaches reaction end, addition 7.62g 4- β-ethyl sulfuryl sulfate ester aniline dry powder into a contracting object, it is warming up to 30~ 35 DEG C, pH value is adjusted to 4~4.5, reacts 7h, detects reaction end using thin-layer chromatography.
(7) two contracting things in above-mentioned (6) coupling reaction: are cooled to 5 DEG C hereinafter, the diazonium prepared in (5) is added later In salt, at 10~15 DEG C, under conditions of pH value is 5.5~6.5, reaction time 7h detects reaction end using thin-layer chromatography.It will Obtained product is dried at a temperature of 65 DEG C, obtains high colour-fast rate reactive dye.Yield 55.3%, dyestuff is through saltouing, DMF- CH2Cl2Recrystallization purification, infrared spectroscopy are shown in Fig. 2.
Dyestuff is in 3373.31cm-1Strong broad peak be N-H and OH stretching vibration formed broad peak；In 2996.38 weak absorptions Peak is CH2Stretching vibration absworption peak；1547.25cm-1Be absorbed as C=N stretching vibration absworption peak；1480.54cm-1Absorption For phenyl ring characteristic absorption peak；1381.71cm-1Be absorbed as C-N stretching vibration absworption peak on iso-indoles ring；1135.06 1087.49cm-1And 1047.71cm-1For the characteristic absorption peak of phthalocyanine ring；739.43cm-1For the stretching vibration peak of C-S and C-Cl； 906.04cm-1For Cu-N vibration absorption peak.
Embodiment 3
The synthesis technology of the following high colour-fast rate mixing chromogen reactive dye of structure:
(1) preparation of copper phthalocyanine sulfonic acid chloride: under room temperature, to three mouthfuls equipped with reflux condensing tube and device for absorbing tail gas 80mL chlorosulfonic acid is added in flask, 15g copper phthalocyanine is added under stiring, then raises temperature to 135 DEG C of reaction 5h, then be cooled to 60 DEG C Thereto be added 22mL thionyl chloride, be warming up to 100 DEG C of reaction 2h, be cooled to later 30 DEG C hereinafter, by system stirring feelings It is slowly added in ice water, filters under condition, filter cake is washed with appropriate ice water, obtains copper phthalocyanine sulfonic acid chloride filter cake 58g.
(2) preparation of the bright blue color base of copper phthalocyanine: the copper phthalocyanine sulfonic acid chloride in step (1) is beaten under the conditions of ice-water bath 1h.Accurately weighing 5.04g 2,4- diamino benzene sulfonic acid sodium salt (double) is made into 15% solution, and adjusting pH value is 6~6.5, by It is added drop-wise in the uniform copper phthalocyanine sulfonic acid chloride of mashing, appropriate pyridine is added and makees catalyst.It is 6.5~7,15~20 DEG C in pH value Under conditions of react 7h, be warming up to 30-35 DEG C of addition 1.03mL ammonium hydroxide reaction 5h, pH value risen into 9~10 temperature later and is risen to 40~45 DEG C of reaction 3h detect reaction end using thin-layered chromatography.
(3) preparation of bright blue one contracting object of color base: the solution that 5.11g Cyanuric Chloride is made into 20% is weighed, in 0~2 DEG C of condition Under 1h is beaten in ice water.Turquoise blue based sols in step (2) are cooled to 5 DEG C hereinafter, pH value is down to 6, instill three dropwise In polychlorostyrene cyanogen, reaction temperature is 0~10 DEG C, and pH value in reaction is 4~5, reaction time 12h, is detected using thin-layered chromatography anti- Answer terminal.
(4) step (3) described contracting liquid preparation of two contracting things: is added in 5.04g 2,4- diamino benzene sulfonic acid sodium salt dry powder In, 35~40 DEG C are warming up to, pH rises to 7~8, reacts 7h, detects reaction end using thin-layered chromatography.
(5) step (4) the two contractings liquid preparation of diazonium salt: is cooled to 5 DEG C hereinafter, 5.20g is added under ice-water bath The concentrated hydrochloric acid solution that mass fraction is 36.5%, 30% aqueous solution that 1.82g sodium nitrite is made into is slowly dropped into 1h, is dripped off 1.5h is reacted under the conditions of -5~0 DEG C afterwards.
(6) preparation of one contracting object and two contracting things of 1- hydroxyl -7- amino -3- naphthalene sulfonic acids: while above-mentioned reaction carries out, claim It takes 5.11g Cyanuric Chloride to be made into 20% solution, is beaten 30min in ice water under the conditions of 0~2 DEG C.By 6.52g1- amino- 8- naphthols -3,6- disulfonic acid is made into 15% solution, adjusts pH 5.8~6.0, instills in Cyanuric Chloride dropwise, at 0~5 DEG C 1.5h is reacted under the conditions of being 3~3.5 with pH value, detects reaction end using thin-layer chromatography.After one contracting reaches reaction end, Xiang Yi 7.62g 4- β-ethyl sulfuryl sulfate ester aniline dry powder is added in contracting object, is warming up to 30~35 DEG C, pH value is adjusted to 4~4.5, reaction 7h detects reaction end using thin-layer chromatography.
(7) coupling reaction: the two contracting things in above-mentioned (6) are cooled at 5 DEG C, and the diazonium salt prepared in (5) is added later In, at 10~15 DEG C, under conditions of pH value is 5.5~6.5, reaction time 7h detects reaction end using thin-layer chromatography.Will To product dried at a temperature of 65 DEG C, obtain high colour-fast rate reactive dye.Yield 58.45%.Dyestuff is through saltouing, DMF- CH2Cl2Recrystallization purification, infrared spectroscopy are shown in Fig. 3.
Dyestuff is in 3319.56cm-1Strong broad peak be N-H and OH stretching vibration formed broad peak；In 2986.91 Hes 2921.82cm-1Weak absorption peak is CH2Stretching vibration absworption peak；1548.60cm-1Be absorbed as C=N stretching vibration absorption Peak；1482.58cm-1Be absorbed as phenyl ring characteristic absorption peak；1391.75cm-1Be absorbed as C-N stretching vibration on iso-indoles ring Absorption peak；1137.76 1087.76cm-1And 1050.90cm-1For the characteristic absorption peak of phthalocyanine ring；740.58cm-1For C-S and C- The stretching vibration peak of Cl；904.12cm-1For Cu-N vibration absorption peak.
Embodiment 4
It is 1.83 × 10 that high colour-fast rate reactive dye in embodiment 1,2,3, which are each configured to concentration,-5mol/L、1.92× 10-5mol/L、1.92×10-5The aqueous solution of mol/L measures the uv-visible absorption spectra curve of each dyestuff, as a result as schemed Shown in 4, and its molar extinction coefficient is calculated, as a result as shown in table 1 below:
Embodiment 5
High colour-fast rate reactive dye in embodiment 1,2,3 are subjected to stamp to cotton fabric, fabric purple can be supplied to respectively, Brown-green, mulberry tone.
Take 5 parts of urea, 1 part of reserve salt, 2.5 parts of sodium bicarbonate, 5 parts of sodium alginate and 86.5 parts of warm water are tuned into paste in container Shape, and being sufficiently stirred makes it uniformly be configured to printing gum.By embodiment 1,2 obtained dyestuffs each 0.5 part (1%), 1 part (2%), 2 parts (4%), 3 parts (6%), 4 parts (8%), respectively with 49.5 parts, 49 parts, 48 parts, 47 parts, 46 parts of above-mentioned printing gum It is uniformly mixed, is modulated into print paste, stamp is carried out to cotton with the printing screen of 200 meshes, bakes 4min at 80 DEG C, 105 DEG C of decatize 8min.It washes, soaps by a large amount of cold water, hot water wash, cold water is dried after washing.Each concentration printing fixation is tested, As shown in figure 5, test its apparent color depth Integ value, as shown in fig. 6, show such turquoise blue dyestuff in stamp, with The increase of dye strength, tinctorial yield step up, and have good improving performance and depth.
Embodiment 6
The stamp cotton fabric that dye strength in embodiment 4 is 4% is subjected to every color fastness test, the present embodiment is referring to mark It is quasi- are as follows: colorfastness to rubbing ISO 105-X12 (2001), color fastness to washing ISO 105-C03 (2010), color fastness to light ISO 105-B02 (2013), test result is as shown in table 2.
Table 2

Claims (10)

1. a kind of double chromogen reactive dye of high colour-fast rate phthalocyanine azo group, it is characterised in that: general structure is as follows:
In formula, 0 < x≤2,0 < y≤2,0 z≤2 <, and x+y+z=3.5~4.
2. the preparation method of a kind of double chromogen reactive dye of high colour-fast rate phthalocyanine azo group, comprising:
(1) under room temperature, chlorosulfonic acid is added into reaction vessel, copper phthalocyanine is added under stirring at room temperature, carries out sulfonation and chlorine Change reaction, after reaction, thionyl chloride reaction is added, reaction system is added in ice water, suction filtration obtains copper phthalocyanine sulphonyl；Its In, the molar ratio of copper phthalocyanine, chlorosulfonic acid and thionyl chloride is 1~2:40~50:20~25；
(2) it by the copper phthalocyanine sulfonic acid chloride wiring solution-forming in step (1) and is beaten, 2,4- diamino benzene sulfonic acid sodium solution and pyrrole is added Pyridine reaction, adding ammonium hydroxide, the reaction was continued, obtains turquoise blue based sols；Wherein, copper phthalocyanine sulfonic acid chloride, 2,4- diamino benzene sulfonic acid The molar ratio of sodium and ammonium hydroxide is 1:1~2:1~3；
(3) it by Cyanuric Chloride wiring solution-forming and is beaten, the turquoise blue based sols being added in step (2) are stirred to react, and obtain a contracting Object；Wherein, the molar ratio of bright blue color base and Cyanuric Chloride is 1:1.02~2.04；
(4) 2,4- diamino benzene sulfonic acid sodium is added in step (3) described contracting object solution and is stirred to react, obtain two contracting things；Its In, a contracting object and 2, the molar ratio of 4- diamino benzene sulfonic acid sodium is 1:1~2；
(5) two contracting things solution described in step (4) is cooled down under ice-water bath, concentrated hydrochloric acid is added, and instill sodium nitrite solution, Being kept for -5~0 DEG C after dripping off, the reaction was continued 1.5~2 hours, obtains diazonium salt；Wherein, two contracting things, concentrated hydrochloric acid and sodium nitrite Molar ratio is 1:2~3:1~2；
(6) it by Cyanuric Chloride wiring solution-forming and is beaten, Rn is added1Solution reaction obtains Rn1One contracting object, is added after the reaction was completed Rn2Dry powder obtains Rn1Two contracting things；Wherein, Rn1, Cyanuric Chloride and Rn2Molar ratio be 1:1.02:1；
(7) it will be added in diazonium salt described in step (5) after the cooling of two contracting things described in step (6), carry out coupling reaction, i.e., It can；Wherein, the molar ratio of diazonium salt and two contracting things described in step (6) is 1:1~2.
3. the preparation method of reactive dye according to claim 2, it is characterised in that: the sulfonation temperature in the step (1) Degree is 130~140 DEG C, and sulfonation time is 3~6h；Chlorination temperature is 90~105 DEG C, and time of chlorinating is 1~3h.
4. the preparation method of reactive dye according to claim 2, it is characterised in that: the copper phthalocyanine in the step (2) The mass fraction of chloride solution is 10~20%, and mashing temperature is 0~5 DEG C, and the time is 50~70min；2,4- diaminobenzene The mass fraction of sodium sulfonate solution is 10%~20%.
5. the preparation method of reactive dye according to claim 2, it is characterised in that: three polychlorostyrene in the step (3) The mass fraction of cyanogen solution is 10~20%, and mashing temperature is 0~2 DEG C, and beating time is 20~40min；Turquoise blue based sols 5 DEG C are cooled to hereinafter, pH value is down to 6 in advance；Reaction temperature is 0~10 DEG C, and adjustings pH value is 3-5, the reaction time for 10~ 12h。
6. the preparation method of reactive dye according to claim 2, it is characterised in that: the reaction temperature in the step (4) Degree is 35~40 DEG C, and adjusting pH value is 7~9, and the reaction time is 7~12h.
7. the preparation method of reactive dye according to claim 2, it is characterised in that: three polychlorostyrene in the step (6) The mass fraction of cyanogen solution is 10~20%, and mashing temperature is 0~2 DEG C, and beating time is 20~40min；One contracting reaction temperature It is 0~5 DEG C, pH value in reaction is 3~3.5, and the reaction time is 1~2h；Two contracting reaction temperatures are 30~35 DEG C, pH value in reaction 4 ~4.5, the reaction time is 5~6h.
8. the preparation method of reactive dye according to claim 2, it is characterised in that: the Rn in the step (6)1For 1- Amino-8-naphthol -3,6- disulfonic acid sodium salt, 2- amino -5- hydroxyl -7- naphthalene sulfonic acids or 1- hydroxyl -7- amino -3- naphthalene sulfonic acids；Rn2 For 4- β-ethyl sulfuryl sulfate ester aniline or 3- β-ethyl sulfuryl sulfate ester aniline.
9. the preparation method of reactive dye according to claim 2, it is characterised in that: the coupling in the step (7) is anti- Answering temperature is 10~15 DEG C, and pH value is 5.5~6.5, and the reaction time is 6~7h.
10. the application of a kind of double chromogen reactive dye of high colour-fast rate phthalocyanine azo group as described in claim 1, feature exist In: power-product is made after spray drying treatment.
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